JPH02129106A - Agrochemical aqueous suspension - Google Patents

Abstract

PURPOSE:To produce the title agrochemical preparation which has good physical properties as a preparation and gives a stable dispersion, even when it is used after dilution with water, by using a dispersant such as an alkali metal salt of specific quinoline carboxylic acid or lignin sulfonic acid. CONSTITUTION:The subject agrochemical preparation is composed of, as an active ingredient, 1-ethyl-1,4-dihydro-6,7-methylenedioxy-4-oxo-3-- quinolinecarboxylic acid which manifests controlling effect against a wide range of bacteria causative of diseases of various kinds of crops and a dispersant of an alkali metal salt, ammonium salt or organic amine salt selected from (A) lignin sulfonic acids, (B) formaldehyde condensates with sulfonated aryl compounds such as naphthalene-sulfonic acid derivative and (C) water-soluble polymer or copolymer composed of unsaturated carboxylic acid such as acrylic acid or maleic acid their derivative as structure units. The amount of the active ingredient is 5 to 50wt.%, and the dispersant is 0.5 to 15wt.%, preferably 1 to 10wt.%.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention provides 1-ethyl-1,4-dihydro-6,7-methylenedioxy-4-oxo-3-quinolinecarboxylic acid (hereinafter referred to as compound A). ) as an active ingredient.

<Prior art and problems to be solved by the invention> Up to now, emulsions, wettable powders, and powders have been widely used as agrochemical formulations for foliage spraying and seed treatment. however,
Since emulsions contain multiple organic solvents, there is a risk of ignition during manufacture, storage, and transportation, and there is also a risk of odor and odor.
They often have drawbacks such as toxicity and irritation to humans, livestock, and small animals, and phytotoxicity to crops. In addition, hydrating powders and powders, which are finely powdered preparations, pose safety problems for workers due to the scattering of fine powder when handled, and when hydrating powders are used diluted with water, they can be used at high concentrations. It has disadvantages such as low volume and difficulty in dispersion.

For the above-mentioned reasons, in recent years, a suspension-type agricultural chemical formulation (hereinafter referred to as a flowable agent) in which a hydrophobic agricultural chemical active ingredient is suspended and dispersed in the form of fine particles using water as a base material has been studied.

On the other hand, Compound A used as an active ingredient of the preparation of the present invention is a compound described in Japanese Patent Publication No. 57-48042, and is a compound that is used for soft rot disease (E, caroto rot) of various extracted vegetables.
vora), potato blackleg disease (E.

atroseptica), apple blight fungus (E.
, amylovorn), solanaceae bacterial wilt (P,
solanacearum), pressure point bacterial disease of cucumber (P, lachrymans), bacterial black spot disease of vegetables (P, syringae pv, macu)
licola), black rot (X, campestr.
is), tumefaciens disease (A.

tumefaciens),) canker sores (C
, michigana-nenSe), rice bacterial blight disease (P, glumae), tobacco wildfire disease (P. glumae),
P. tabaci), citrus canker disease (X.

campes) rice leaf blight (X, ory
zae), rice lateral streak disease (P, avenae)
, peach borer bacterial disease (X.

It is a plant control agent that exhibits excellent control effects against a wide range of bacterial diseases of various crops, including P. vesicatoria).

However, when Compound A is formulated using conventional flowable formulations, (11) it is greatly influenced by cations in water, especially polyvalent cations such as calcium ions and magnesium ions
Cannot be formulated into a flowable agent.

(Dry) When the obtained flowable agent is diluted with water and used, agglomeration occurs and a stable spray solution cannot be obtained.

There are problems such as:

Means for Solving the Problems> Therefore, as a result of intensive studies on the flowable agent of Compound A, the present inventors used Compound A as an active ingredient, (a) lignin sulfonic acid, and (0) sulfonated aroma. A group of compounds consisting of formalin condensates of group compounds and water-soluble polymers or water-soluble copolymers (hereinafter referred to as carboxylic acid polymers) whose constituent monomers are f-4 unsaturated carboxylic acids or derivatives thereof. Alkali metal salts (e.g., sodium salts,
potassium salts), ammonia, murine salts and organic amine salts (
For example, an aqueous suspension agricultural chemical formulation (hereinafter referred to as the formulation of the present invention) containing as a dispersant (hereinafter referred to as the dispersant of the present invention) a dispersant (for example, a jetanolamine salt, a triethanolamine salt, etc.) ) was found to have excellent properties as a pharmaceutical preparation, and after further study, the present invention was arrived at.

This invention: The lignin sulfonic acid used in this invention is a water-soluble polymer obtained by sulfonating lignin, which is the main component of wood, and can be used regardless of the type of wood used as a raw material or the manufacturing method. can.

The formalin condensate of a sulfonated aromatic compound used in the present invention is a formalin condensate of a naphthalene sulfonic acid derivative, a xylene sulfonic acid derivative, an alkylbenzenesulfonic acid derivative, etc., and usually has an average degree of condensation of 8 to 8.
0 is used.

The carboxylic acid polymers used in the present invention include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, and derivatives thereof.
(e.g., alkyl esters thereof, etc.),
Alternatively, copolymers of the above-mentioned unsaturated carboxylic acids and copolymerizable therewith, such as styrene, isobutylene, vinyl acetate, etc., and mixtures thereof can be mentioned. More specifically, examples include copolymers of maleic acid and styrene, copolymers of maleic acid and isobutylene, copolymers of maleic acid and acrylic acid, and copolymers of methyl acrylate and vinyl acetate. Examples include compounds and mixtures thereof. Although the degree of polymerization and the ratio of monomer components of these polymers are not particularly limited, it is necessary that the alkali metal salt, ammonium salt, and organic main salt of these polymers are water-soluble.

The formulation of the present invention optionally contains alkali metal salts, ammonium salts, organic amine salts of ionic surfactants such as alkyl sulfates, alkylbenzenesulfonic acids, dialkyl sulfosuccinates, alkyl phosphates, and polyoxyethylene. Nonionic surfactants such as alkyl ethers, polyoxyethylene alkyl allyl ethers, and sugar fatty acid esters can also be used as dispersion aids.

Furthermore, if necessary, water-soluble polymers such as xanthan gum, cellulose island conductor, Aerosil, smectite clay, etc. may be used as thickeners, antifreeze agents such as ethylene glycol, glycerin, propylene glycol, and preservatives such as formalin. etc. can also be used.

The formulation of the present invention contains 5 to 50 copies of Compound A and 0.6 to 16% of the dispersant of the present invention, preferably 1 to 10% by weight.
If necessary, other dispersion aids, thickeners, antifreeze agents, preservatives, etc. may be added, and the remaining amount may be water.

An example of a method for formulating the preparation of the present invention will be described below, but the method is not limited to this.

That is, in the preparation of the present invention, compound A is jet milled,
Grind into a fine powder using a dry grinder such as a hammer mill or pin mill,
This can be obtained by dispersing this in an aqueous solution containing the dispersant of the present invention, and adding other dispersion aids, thickeners, antifreezes, preservatives, etc. as necessary. Also, compound A
is added to an aqueous solution containing the dispersant of the present invention and other dispersion aids as necessary, and pulverized with a wet pulverizer such as a sand mill, colloid mill, or dyno mill, and further added with a thickener and an antifreeze agent as necessary. It can also be obtained by adding

The preparation of the present invention can be used in various forms, such as directly or diluted with water and sprayed on grass, mixed with soil and irrigated, or applied to seeds. Furthermore, by mixing it with other plant disease control agents, it can be expected that the control efficacy will be enhanced. In addition, insecticides, acaricides, nematicides, herbicides, plant growth regulators,
It can also be used in combination with fertilizers, soil conditioners, etc.

The particle size of Compound A in the formulation of the present invention is not particularly limited, but from the viewpoint of stability during storage of the formulation and uniformity of dispersion, the average particle size is preferably 5 μm or less.

<Effects of the Invention> The formulation of the present invention has good physical properties as a formulation, and a stable dispersion can be obtained even when diluted in a water bottle, making it extremely useful as an agricultural chemical formulation. .

<Examples> The present invention will be described in more detail below with reference to formulation examples, comparative examples, test examples, and biological test examples, but the present invention is not limited to these examples.

Please note that the division is the Heavy Electrical Department.

Formulation Example 1 25 parts of Compound A, 2 parts of REAX 85A (sodium ligninsulfonate, manufactured by West Virco), and ion-exchanged water were added to make a total volume of 60 parts, and the mixture was made using a sand grinder (manufactured by Igarashi Kikai) using 1+aφ glass beads 80y. The mixture was wet-pulverized for 8 hours using a grinder (manufactured by ①) for 8 hours. The glass beads were then separated using a 60-mesh nylon screen to obtain a pulverized liquid of Compound A.

On the other hand, 1 part of Echo Gum (Xanthan Gum: manufactured by Dainippon Pharmaceutical Co., Ltd.), Vee Gum (Smectite Clay: R, T).

A thickener solution (hereinafter referred to as thickening agent) was prepared by dissolving and dispersing 2 parts (manufactured by anderbi It) in 97 parts of ion-exchanged water.

The same applies to the following four formulations and comparative examples. ) was prepared. 20 parts of the pulverized liquid of compound A obtained in
Further, ion-exchanged water was added to make Kanaya 1θθ, and a 26% flowable agent was obtained for the compound.

Formulation Example 2 50 parts of Compound A, 4 parts of Osan HP (sodium lignin sulfonate: manufactured by Sankyo Kasei ■), and ion-exchanged water were added to make the total amount 90 parts, and 100 parts of 1-diaphragm glass beads were added.
A pulverized liquid of Compound A was obtained by the same operation as in Formulation Example 1 using y. Adding 910 parts of a thickener to this, compound A
A 50% flowable agent was obtained.

Formulation Example 3 10 parts of Compound A, 2 parts of Osan CD (sodium lignin sulfonate: manufactured by Sankyo Kasei ■), and further added ion-exchanged water to make a total of 25 parts, 1 piece of φ Glass Peas 802
A pulverized solution of the compound was obtained in the same manner as in Formulation Example 1. Add to this 80 parts of thickener liquid and 10 parts of ethylene glycol.
part, further add ion exchange water to make the total amount 100 parts,
A 10% flowable agent of Compound A was obtained.

! ! ! Cutting example 4 Compound A 25 parts, Ozan HP (above) 2 cities, 5 OPs
Add 2 parts of ROPHOL FL (phosphoric acid ester surfactant Nirone, manufactured by Boulin) and ion-exchanged water to make the total amount 6.0 parts, and perform the same operation as in Formulation Example 1 to obtain a pulverized liquid of Compound A. Ta. To this, 20 parts of thickener liquid and further ion exchange water were added to make the total amount 100 parts, and compound A
A 26% flowable agent was obtained.

Formulation Example 5 Same as Formulation Example 1, adding 25 parts of Compound A, 7 parts of Ozan HP (above), 1 part of Tsurpol 8048 (nonionic surfactant: manufactured by Toho Katei), and further adding ion-exchanged water to make a total of 60 parts. The pulverization number of compound A was obtained by the following operation. 20 parts of a thickener liquid and further ion-exchanged water were added to make the total amount 100 parts to obtain a flowable agent for Compound A 25.

Formulation Example 6 A 25% flowable agent of Compound A was prepared in the same manner as in Formulation Example 1 except that Demol SNB (sodium salt of special aromatic sulfonic acid formalin condensate: manufactured by Kao) was used in place of REAX 85A. I got it.

Formulation Example 7 In Formulation Example 1, GER instead of REAX 85A
A 25% flowable agent of Compound A was obtained in the same manner as in Formulation Example 1 using OPON SC/211 (sodium salt of carboxylic acid copolymer: manufactured by Boulin, Rhône).

Formulation example 8 Formulation example! , GER instead of REAX 85A
A 26% flowable agent of Compound A was obtained in the same manner as in Formulation Example 1 using OPON SC/211 (potassium salt of carboxylic acid copolymer: manufactured by Boulin, Rhône).

Formulation Example 9 In Formulation Example 1, DIS was used instead of REAX 85A.
A 25% flowable agent of Compound A was prepared in the same manner as in Formulation Example 1 using 2 parts of PER5ANT DA (water-soluble Kl of triethanolamine salt of acrylic acid copolymer: manufactured by Rhone and Boulin) in terms of solid content. I got it.

Formulation Example 10 In Formulation Example 1, 5OP instead of REAX 85A
Using ROPON T/86 (sodium salt of carboxylic acid polymer: Rhone, manufactured by Boulin), a 26% flowable agent of Compound A was obtained in the same manner as in Formulation Example 1.

Comparative Example 1 In Formulation Example 1, 5an instead of REAX 85A
X P-201 (calcium salt of ligninsulfonic acid:
When wet pulverization of Compound A was attempted in the same manner as in Formulation Example 1 using Sanyo Kokusaku Pulp (manufactured by Sanyo Kokusaku Pulp), a pulverized liquid of Compound A could not be obtained because the entire pulverized liquid became immobilized.

Comparative Example 2 A 25% flowable agent of Compound A was obtained in the same manner as in Formulation Example 1 except that GOHSENOL GL-05 (polyvinyl alcohol: manufactured by Nippon Gohsei) was used in place of REAX 85A.

Comparative Example 8 In Formulation Example 1, 5OP was used instead of REAX 85A.
A 25% flowable preparation of Compound A was obtained using ROPHOL FL (described above) in the same manner as in Formulation Example 1.

Comparative Example 4 A flowable agent for Compound A 25 was obtained in the same manner as in Formulation Example 1, except that Trupol 8048 (Letter II) was used in place of REAX 85A.

Comparative Example 5 In Formulation Example 1, Compound A was prepared in the same manner as in Formulation Example 1, except that 2 parts of Tsurpol 7510 (aqueous solution of sulfonic acid surfactant: manufactured by Toho Katei Co., Ltd.) was used in place of REAX 85A. A flowable agent was obtained on the 26th.

Comparative Example 6 In Formulation Example 1, 25% flowable of Compound A was obtained by the same operation as Formulation Example 1, except that Tsurpol 8078 (anionic/nonionic surfactant mixture: Toho Ka Handicraft) was used instead of REAX 85A. obtained the drug.

Comparative Example 7 Formulation Example 1 (herein, 25% flowability of Compound A was carried out in the same manner as in Formulation Example 1, using Tsurpol 8741 (anionic surfactant mixture: Toho Katei Seibu) instead of REAX 85A. obtained the drug.

Test Example 1 The obtained flowable agent was placed in a Coulter Counter TAn.
The average particle diameter of Compound A was determined using a mold (Coulter, manufactured by Electronics Co., Ltd.), and the viscosity was measured using a Type B Chodanmeter (manufactured by Tokyo Seiki, rotors 1 & 8.6 rotations) to evaluate the ease of handling of the preparation. did.

The test results are shown in Table 1.

Table 1 Test Example 2 The dispersion stability of the obtained flowable agent after dilution with water was evaluated by determining the suspension ratio using the following method.

According to the following formula Find the suspension rate.

The test results are shown in Table 2.

Precisely weigh sample 2.57 in Table 2 into a beaker and place it in CI PA at 30°C.
C-titled water D (MT 18.1.4.CIPACHA
NDBOOK) 100- is added and dispersed. That 2
Transfer to a 50-℃ stoppered cylinder and store at 80℃ CI PAC.
After increasing to 250- with standard water, 80 per minute
The cylinder is violently overturned and dispersed. Immediately, 25
．． , T/ is placed in a cylinder so that its tip is in the center of the liquid, and 25ml of the test liquid is taken in 1% I. Transferred to a glass petri dish and dried at 110°C for 2 hours.
Measure the solid weight in the test solution (Sg). On the other hand, after the cold liquid has been removed, the cylinder is left to stand in a constant temperature water bath at 30°C for 80 minutes, and then the solid weight in the dispersion center 25 is measured in the same manner as described above. Bg).

Next, a biological efficacy test was conducted using the obtained formulation examples and comparative examples.

Biological test example 1 Potato blackleg disease efficacy test formulation examples 1-1
0 and Comparative Examples 2 to 8 were diluted with water to a predetermined concentration and allowed to stand for 1 hour, and then the upper half of this suspension was sprayed on potatoes (Baron) so that they were sufficiently adhered to the surface. After spraying, potato blackleg fungus was inoculated into the wound. Sow it in sandy loam soil,
Cultivated in a greenhouse for days. Thereafter, the tubers were dug over and the disease state was investigated for each potato, and the percentage of healthy tubers was calculated using the following formula.

The results are shown in Table 8.

Biological Test Example 2 Effect on Controlling Bacterial Rice Blight Disease Wagner pots K-IR were filled with sandy loam, and rice (Kinki No. 88) was grown in a greenhouse for 80 days and headed. After that, Formulation Examples 1 to 1
0 and Comparative Examples 2 to 8 were diluted with water to a predetermined concentration and allowed to stand for 1 hour, and then the upper half of the suspended branches was sprayed so as to sufficiently adhere to the panicle surface. After spraying, a spore suspension of rice bacterium was inoculated by spraying. After inoculation, the plants were kept in a humid environment for about 24 hours, and then grown for another 7 days under the above greenhouse conditions.

Thereafter, the disease state of each grafted crane was investigated according to the following investigation criteria.

In addition, the control value was calculated using the following formula, and the results were expressed as follows: Biological Test Example 8 Chinese cabbage soft rot control test Plastic pots were filled with sandy loam, Chinese cabbage (60-day Chinese cabbage) was sown, and grown in a greenhouse for 80 days. After that, Formulation Examples 1 to 10
Comparative Examples 2 to 8 were diluted with water to a predetermined concentration and left to stand for 1 hour, and then the upper half of this suspension was sprayed on foliage so as to sufficiently adhere to the leaf surface. Thereafter, a spore suspension of Chinese cabbage soft rot was inoculated. After inoculation, the plants were kept in a humid environment for about 6 p.m., and then grown for one day under the above greenhouse conditions. after that,
The disease state was investigated for each inoculated leaf.

The investigation method was as follows.

That is, the disease severity is determined by determining the disease attack area rate of the investigated leaves, classifying it into 0.0.6.1.2.4 indices according to the degree, and calculating the number of leaves corresponding to each disease attack index. , 73, η, Misaki was investigated and calculated using the following formula, and then the control value was determined.

The results are shown in Table 5.

Claims (3)

[Claims] (1) 1-ethyl-1,4-dihydro-6,7-methylenedioxy-4-oxo-3-quinolinecarboxylic acid as an active ingredient, (a) ligninsulfonic acid, (b) sulfonated aromatic compound and (c) an alkali metal salt, ammonium salt, or organic amine of a compound selected from the group consisting of a water-soluble polymer or a water-soluble copolymer whose constituent monomer is an unsaturated carboxylic acid or a derivative thereof. An aqueous suspension of an aqueous pesticide formulation containing one or more salts as a dispersant. (2) 1-ethyl-1,4-dihydro-6,7-methylenedioxy-4-oxo-3-quinolinecarboxylic acid,
The aqueous suspension pesticide formulation according to claim 1, wherein the amount of the dispersing agent is 0.5 to 15% by weight. (3) A method for controlling plant pathogenic bacteria, which comprises treating the plant pathogenic bacteria with the aqueous suspension of the agricultural chemical formulation according to claim 1 or 2.